A Kinetic Study of Titanium Nitride Chemical Vapor Deposition Using Nitrogen, Hydrogen, and Titanium Tetrachloride

Abstract

The kinetics of the growth of titanium nitride (TIN) by hot-wall atmospheric pressure chemical vapor deposition (CVD) has been studied using titanium tetrachloride (TIC14), hydrogen (H2), and nitrogen (N~) as reactants. The growth rate as a function of reactant concentration at different reaction temperatures is determined. The growth rate dependence in the TiC14 input concentration changes from a positive to a negative order behavior with increasing reactant concentration, and the observed maximum growth rate shifts to a higher TiC14 input concentration with increasing reaction temperature. For the growth rate a square root dependence in the N2 concentration is observed in all cases, and for the growth rate a positive order dependence in the H2 concentration is observed which changes from 0.5 to 1.5. A reaction model has been proposed based on isothermal Langmuir adsorption behavior with mutual displacement on titanium sites at the surface, and an indirect mutual displacement on nitrogen sites at the surface. This reaction model consists of a set of elementary gas-phase, adsorption, and surface reactions which are quasi-equilibrated, and a rate-determining step involving the reaction at the surface between an adsorbed TIC13 species on a nitrogen site, and an adsorbed NH species on a titanium site. Using this model the experimental and reported growth rate data can be understood as a function of reactant concentration within the temperature region from 1000 to 1273 K.Chemical vapor deposition (CVD) is a well-known synthesis method for producing titanium nitride (TIN) layers. 1-2~ These TiN layers are used, because of their electrical conductivity, 2-8 or structural properties such as wear and corrosion resistance. 7-9 TIN layers can be used as a diffusion barrier between metal and silicon in electronic circuits. 2-4 These layers are deposited in a cold-wall low-pressure CVD apparatus at substrate temperatures between 600 and 900 K using titanium tetrachloride (TiC14), ammonia (NH3), and hydrogen (H2) according to reaction 12-6

Preparation and characterization of CVD-TiN-coated carbon fibers for applications in metal matrix composites

“…E A values between 116 and 163 kJ/mol were obtained. These activation energies are in fairly good agreement with values of 108 kJ/mol and 100-183 kJ/mol reported by Popovska et al [15] and Dekker et al [28] for the surface controlled range. Fig.…”

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“…8 At high substrate temperatures TiN films have been grown from TiCl 4 and a nitrogen/hydrogen mix (1100 uC). 9 The other early transition metal nitrides, including VN, NbN, TaN, HfN, ZrN all have predominant fcc-NaCl phases with similar properties to TiN. 10 There are comparatively fewer reports of the growth of these latter materials by CVD.…”

Chemical vapor deposition of titanium nitride thin films: kinetics and experiments

“…To the date, it is still difficult to predict which process conditions will lead to a certain texture or visual aspect in TiN due to discrepancies in the effect of parameters according to different authors and scattered data. In general, the growth rate is positively affected by increasing H2, N2, and NH3 partial pressures but a positive to negative dependence of growth rate to increasing TiCl4 partial pressure is observed in literature [17,21]. It results from the formation of a non-reactive complex, TiCl4NH3 in the gas phase.…”

“…Chemical Vapor Deposition (CVD) [13] is a common technique for the growth of TiN thin films [5,6,12,[14][15][16]. Particularly, two major chemical systems for the thermal CVD of TiN coatings, TiCl4-N2-H2 and TiCl4-NH3-H2, are used [17]. The temperature range for the first system is 900-1200 °C due to the low reactivity of nitrogen [18].…”

“…A global kinetic model of TiN growth from TiCl4-N2-H2 system was proposed in Ref. [17,21]. A detailed kinetic mechanism and reaction pathways were built for the TiCl4-NH3-H2 system by Larson et al and Allendorf et al [22,23], but only for a temperature of 630°C.…”